Eur. J. Mineral., 32, 623–635, 2020 https://doi.org/10.5194/ejm-32-623-2020 © Author(s) 2020. This work is distributed under the Creative Commons Attribution 4.0 License. Contribution to the crystal chemistry of lead-antimony sulfosalts: systematic Pb-versus-Sb crossed substitution in the plagionite homologous series, Pb2N−1(Pb1−xSbx/2(Sb1−xPbx/2Sb6S13C2N Yves Moëlo1 and Cristian Biagioni2 1Institut des Matériaux Jean Rouxel (IMN) – UMR 6502, Université de Nantes, CNRS, 44000 Nantes, France 2Dipartimento di Scienze della Terra, Università di Pisa, Via S. Maria 53, 56126 Pisa, Italy Correspondence: Yves Moëlo ([email protected]) Received: 5 July 2020 – Revised: 1 October 2020 – Accepted: 16 October 2020 – Published: 14 November 2020 Abstract. The plagionite homologous series contains four well-defined members with the general formula Pb1C2N Sb8S13C2N : fülöppite (N D 1), plagionite (N D 2), heteromorphite (N D 3), and semseyite (N D 4). The crystal structure of several natural and synthetic samples of fülöppite, plagionite, and semseyite have been refined through single-crystal X-ray diffraction, confirming the systematic Pb-versus-Sb crossed substitution observed previously in semseyite and fülöppite. This crossed substitution takes place mainly in two adjacent cation sites in the middle of the constitutive SnS-type layer. The substitution coefficient x appears variable, even for a given species, with the highest values observed in synthetic fülöppite samples. The developed structural formula of the plagionite homologues can be given as Pb2N−1(Pb1−xSbx/2(Sb1−xPbx/2Sb6S13C2N . In the studied samples, x varies between ∼ 0.10 and 0.40. In the ribbons within the SnS-type layer, (Pb=Sb) mixing can be considered the result of the combination, in a variable ratio, of two cation sequences, i.e. (Sb–Sb–Sb)–Pb–Sb–(. ), major in pla- gionite and semseyite, and (Sb–Sb–Sb)–Sb–Pb–(. ), major in fülöppite and, probably, in heteromorphite. The published crystal structure of synthetic “Pb-free fülöppite” is revised according to this approach. It would corre- spond to a Na derivative, with a proposed structural formula of (Na0:5Sb0:5/(Na0:2Sb0:8/2(Na0:3Sb0:7/2Sb6S15, ideally Na1:5Sb9:5S15. In fülöppite, increasing x induces a flattening of the unit cell along c, with a slight volume decrease. Such a general Pb-versus-Sb crossed substitution would attenuate steric distortions in the middle of the SnS-type layer of the plagionite homologous series. Crystallization kinetics seem the main physical factor that controls such an isochemical substitution. Dedicated to the memory of Dr. Nadejda N. Mozgova opposition to “acicular lead sulfosalts”, e.g. boulangerite, (1931–2019), Russian mineralogist of the Institute of zinkenite, and jamesonite (Spencer, 1899). The comparison Geology of Ore Deposits (IGEM Moscow), specialist of of parameter ratios through goniometric measurements led sulfosalt systematics. Spencer (1899) to the definition of a morphotropic series, a precursor concept of the modern definition of homologous 1 Introduction series. The crystal structures of these four members were re- solved during the 1970s, i.e. plagionite from Wolfsberg, Plagionite, Pb5Sb8S17, defined by Rose (1833), is the chief member of one of the oldest groups of sulfosalts, along with Germany (Cho and Wuensch, 1970, 1974); semseyite (Ko- hatsu and Wuensch, 1974a); fülöppite from Baia Mare (pre- fülöppite Pb3Sb8S15, heteromorphite Pb7Sb8S19, and sem- viously known as Nagybánya), Romania (Edenharter and seyite Pb9Sb8S21. On the basis of their crystal morphology, they were initially described as “tabular lead sulfosalts”, in Nowacki, 1974, 1975a; Nuffield, 1975); and heteromorphite Published by Copernicus Publications on behalf of the European mineralogical societies DMG, SEM, SIMP & SFMC. 624 Y. Moëlo and C. Biagioni: Pb-versus-Sb substitution in the plagionite series from Wolfsberg, Germany (Edenharter and Nowacki, 1975b; cording to modules of increasing dimensionality: 0D (finite Edenharter, 1980). Swinnea et al. (1985) described the crys- groups), 1D (chain, ribbon, column), 2D (slab, layer), and 3D tal structure of a synthetic Pb-free analogue of fülöppite (in (whole structure). Each module can be symbolized by its 3D fact a Na-substituted fülöppite derivative – see below). polyhedra width. For instance, symbol 2=3=1 would corre- A detailed crystal chemical analysis permitted Kohatsu spond to a ribbon, two-polyhedra thick and three-polyhedra and Wuensch (1974b) to develop a general structural scheme large. for this group. This study can be considered the basis for Application of modular analysis to the plagionite series the modern definition of the plagionite homologous series, permits five organization levels to be distinguished, from the Pb1C2N Sb8S13C2N , with the following members: fülöppite bottom, i.e. polyhedra around metal or S atoms (level 1 – (N D 1), plagionite (N D 2), heteromorphite (N D 3), and 3D symbol 1=1=1; see the example of the plagionite struc- semseyite (N D 4). Takéuchi (1997), as part of his general ture in Cho and Wuensch, 1974), up to the top, i.e. the whole study of tropochemical cell twinning, gave considerable de- structure (level 5 – dimensionality 1=1=1/. Level 4 cor- tail about the crystal chemistry of the plagionite series. Re- responds to a layered organization (Kohatsu and Wuensch, cently, Makovicky (2019) presented this series as an example 1974b), with a single type of layer stacking along c with two of a homologous series among sulfosalts. orientations according to the binary axis. These layers cor- In nature, this series has very simple chemistry. Fluctua- respond to diagonal slabs of the SnS archetype (Makovicky, tions in the Pb=Sb atomic ratio correspond to microscopic 1989), with a distortion referring more exactly to the TlSbS2 or submicroscopic lamellar syntactic intergrowths (Mozgova archetype (Takéuchi, 1997; Matsushita, 2018). Layer width and Borodaev, 1972; Moëlo, 1983) visible in crossed polars increases with the homologue number N, through the addi- in reflected light or with SEM imaging. Rarely, arsenic may tion of Pb polyhedra, corresponding to the stacking of (4 Sb substitute for antimony (up to ∼ 10 at. %–12 at. % in plagion- CN Pb) cations (dimensionality (4 CN/=1=1/. Layers are ite from Rujevac, former Yugoslavia; Jankovic´ et al., 1977; connected by an additional Pb atom. Moëlo et al., 1983). Other erratic minor components detected Figure 1 represents the layered structure of fülöppite along by electron microprobe analysis would correspond to impuri- b (Nuffield, 1975). Projection according to [110] or [110] re- ties. Rayite, (Ag,Tl)2Pb8Sb8S21, was defined as an (Ag,Tl)- veals ribbon stacking within each layer. Each ribbon is two rich derivative of semseyite (Basu et al., 1983) on the basis atoms thick, six cations large (Fig. 1c – four Sb and two of its X-ray powder diffraction (XRPD) pattern, but this in- Pb, including the Pb atom at the margin – dimensionality terpretation was later debated (Roy Choudury et al., 1989; 2=6=1). Projection of a single ribbon perpendicular to its Bente and Meier-Salimi, 1991), and crystal structure data are flattening (see Fig. 1c) indicates oblique 2-atom-thick × 2- still lacking. atom-thick rows (Fig. 2), with a finite length of six atoms Re-examination of the original structural data for fülöppite (level 2 – dimensionality 2=2=6). In a row ([110] direction of (Nuffield, 1975) led Swinnea et al. (1985) to highlight minor PbS archetype), there are two cation sequences, Sb–Sb–Sb– Sb substitution in a Pb site, coupled with the reverse substitu- Sb–Pb–Pb and its reverse one. Nevertheless, this approach tion of Pb in an adjacent Sb position. A similar Pb-versus-Sb at level 2 is incomplete. Due to the stereochemical activity crossed substitution was obtained on semseyite from Wolfs- of its lone electron pair, trivalent Sb shows a dissymmetric berg by Matsushita et al. (1997) and recently refined and de- coordination, with three strong Sb–S bonds (i.e. SbS3 poly- tailed by Matsushita (2018). hedra with eccentric triangular pyramidal coordination). In During the systematic study of sulfosalt mineralogy in ore the plagionite series, SbS3 polyhedra coalesce to form finite deposits of the Apuan Alps, a new occurrence of plagionite groups (polymers), which have been described in fülöppite was identified in the baryte C pyrite C iron oxide deposit of and plagionite by Edenharter and Nowacki (1974) and in the Monte Arsiccio mine (e.g. Costagliola et al., 1990). Its heteromorphite and semseyite by Edenharter (1980). These crystal structure study, together with those of other samples groups are represented in Fig. 3, along with neighbouring Pb of plagionite (natural), fülöppite (natural and synthetic), and atoms. They are symmetric across the layer boundary via 2- semseyite (natural) allowed confirmation that such a Pb=Sb fold rotation (2-fold axis parallel to b – see projection along crossed substitution is a general feature of members of the b in Fig. 1). Whereas in fülöppite, plagionite, and heteromor- plagionite homologous series. Detailed results are presented phite, all Sb sites are connected in an Sb8Sm group (Fig. 3a– here. c), in semseyite there is an Sb6S13 group with two isolated SbS3 polyhedra (Fig. 3d). Plagionite, heteromorphite, and semseyite present the 2 Modular description of crystal structures in the same cleavage plane according to f112g. It corresponds to plagionite series the flattening of the ribbons according to (100)PbS. It has not been observed up to now in fülöppite but ought to be present Modular analysis constitutes a powerful approach for the for the same structural reasons. bottom-up description of complex crystal structures of lead sulfosalts, taking into account polyhedra connection ac- Eur. J. Mineral., 32, 623–635, 2020 https://doi.org/10.5194/ejm-32-623-2020 Y. Moëlo and C. Biagioni: Pb-versus-Sb substitution in the plagionite series 625 Figure 1. Crystal structure of fülöppite: projection along b (b),[110] (a), and [110] (c).